Carbodiimide-isocyanurate foams containing urethane linkages

ABSTRACT

Carbodiimide-isocyanurate foams containing urethane linkages are prepared by mixing a polyisocyanate, a polyol and a catalyst system comprising an s-triazine compound and a catalyst which promotes urethane linkages. The resulting foams are characterized by low friability and good flame resistance.

U United States Patent 3,891,578 Kan et al. June 24, 1975 [54]CARBODllMlDE-ISOCYANURATE FOAMS 3,806,475 4/1974 Narayarl et a1 260/25BF CONTAINING URETHANE LINKAGES FOREIGN PATENTS OR APPLlCATlONS 1lflvemorsl Peter Plymouth; 9 1,223,415 2/1971 United Kingdom 260/25 AWCenker, Trenton, both of MlCh.

[73] Assignee: BASF Wyandotte Corporation, Primary ExaminerDonald E.Czaja Wyandotte, Mich. Assislant ExamI'nerC. Warren lvy I Attorney,Agent, or Firm.loseph D. Michaels; [22] 1973 Bernhard R. Swick; RobertE. Dunn {2|} Appl. No.: 425,270

[57] ABSTRACT [52] U.S. CL. 260/25 AC; 260/25 AW; 260/25 BF [51] Int CL.Cosg 22/36; Cosg 22/34; Cosg 33/04 Carbodumide-isocyanurate foamscontaining urethane [58] Field of Search... 260/25 BF 2.5 AW, 2.5 AClmkages are Prepared by a PP a polyol and a catalyst system comprisingan s-triazine [56] Re'erenm Cited compound and a catalyst which promotesurethane linkages. The resulting foams are characterized by low UNITEDSTATES PATENTS friability and good flame resistance. 3,634,345 l/l972Diehr et a]. 260/25 AW 3,723,366 3/I973 Kan 260/25 BF 10 Claims, NoDrawings CARBODIIMIDE-ISOCYANURATE FOAMS CONTAINING URETHANE LINKAGESBACKGROUND OF THE INVENTION l. Field Of The Invention The presentinvention relates to cellular foam compositions characterized by lowfriability and good flame resistance. More particularly, the inventionrelates to carbodiimide-isocyanurate foams containing urethane linkagesprepared by mixing a polyisocyanate and a polyol in the presence ofcertain co-catalyst systems.

2. Prior Art The preparation of foams containing carbodiimide linkagesis well known in the art. Generally, the foams are prepared bycondensing an organic polyisocyanate with a catalyst which promotescarbodiimide linkages, optionally in the presence of a blowing agent.Representative of such teachings are the disclosures found in US. Pat.Nos. 2,94l,966 and 3,645,923. The prior art also teaches that foamscontaining both carbodiimide and isocyanurate linkages can be preparedby condensing an organic polyisocyanate with a catalyst which promotesboth carbodiimide and isocyanurate linkages or with a co-catalystsystem, one catalyst promoting carbodiimide linkages and one catalystpromoting isocyanurate linkages. Representative of such teachings arethe disclosures found in US. Pat. Nos. 3,645,923; 3,657,161; 3,7l7,596;3,723,366, and 3,746,709. Carbodiimide foams containing urethanelinkages are also known in the art as evidenced by U.S. Pat. No.3,772,217. Generally, these foams are prepared by either adding a polyolto the organic poly isocyanate at time of mixing for foaming (one-shotprocess) or using a prepolymer containing pre-formed urethane linkages.There are several inherent disadvantages in either of these processes.

In the one-shot process. there are three reactions, namely,trimerization, carbodiimide and urethane formation occurring almostsimultaneously. The trimerization is usually the most rapid one,followed by carbodiimide and urethane formation. All reactions competefor the use of the isocyanate group. As a result, the extent of theslower urethane fr rmation is diff Pill to predict and, accordingly, theimprovement in physical properties of the resulting foams attributableto urethane formation is not uniformly achieved. The prepolymer processeliminates the problem of urethane reaction competing with the otherfaster reactions; however, the preparation of the prepolymer is oftentedious and the stability of the resulting prepolymer is generally poor.

SUMMARY OF THE INVENTION The present invention relates to an improvedprocess for the preparation of carbodiimide-isocyanurate foamscontaining urethane linkages employing a catalytically sufficient amountof a catalyst which promotes carbodiimide and isocyanurate linkages anda catalyst which promotes urethane linkages. Upon mixing apolyisocyanate, a polyol and the catalysts, the urethane formationreaction due to the presence of a urethane catalyst is both rapid andexothermic. The heat generated from this reaction then activates thecarbodiimide catalyst to cause blowing and foam formation.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As mentioned above, theco-catalyst system employed in the present invention comprises ans-triazine compound which promotes carbodiimide and isocyanuratelinkages and a catalyst which promotes urethane linkages. Representativecatalysts which promote carbodiimide and isocyanurate linkages which areof use in the present invention include: 2,4,6-tris(diethanolamino)-s-triazine. 2,4,6-tris( diisopropanolamino )-s-triazine, 2.4,6-tris(N-methylethanolamino)-s-triazine, and unsymmetrically substitutedtriazines of the formula:

| l CR CR 0H wherein R is hydrogen or lower alkyl of from l to 10 carbonatoms, R is CR CR OH or lower alkyl of from I to 12 carbon atoms, X isNR alkoxy of from I to 12 carbon atoms, phenoxy atoms, alkyl of from lto l2 carbon atoms, phenyl, hydroxyl, halogen, aziridyl, pyrrolidyl,piperidyl, or N-alkylpiperazyl. Since the triazines are unsymmetricallysubstituted, it is apparent that each X cannot concurrently be CRQCREOHN wherein each R and R is the same. Representative compounds from theabove generic formula include:

2-amino-4,6bis(N-methyl-Z-hydroxyethylamino)- l,3,5-triazine,

2.4-bis( N-methyl-2 hydroxyethylamino -6-methoxy- 1,3 ,5 --triazine,

2,4-bis(di 2-hydroxyethylamino )-6-chlorol ,3,5-

triazine,

2,4-bis(N-methyl-2-hydroxyethylamino)-6-chloro- 1,3,5-triazine,

2 ,4-bis( N-methyl-Z-hydroxyethylamino)-6-phenyl- 1,3,5-triazine,

2,4-bis( N-methyl-Z-hydroxyethylamino)-6-diethylamino-l ,3,5-triazine,

2,4-bis( N-methyl-Z-hydroxyethylamino )-6-dimethylaminol ,3,5-triazine2,4-bis(di-Z-hydroxyethylamino)-6-diethylamino- L3 ,5 -triazine,

2,4-bis( di-Z-hydroxyethylamino)-6-phenoxy-l ,3 ,5-

triazine,

2,4-bis(N-methyl-2-hydroxyethylamino)-6-phenoxy- 1,3,5triazine,

2,4-bis( N-methyl-Z-hydroxyethylamino)-6-methyll,3,5-triazine,

2,4-bis(di-Z-hydroxyethylamino)-6-methyl-1,3,5-

triazine,

2,4-bis( N-methyl-2-hydroxyethylamino)-6-hydroxyl ,3,5-triazine,

3 2,4-bis(diethylamino)-6-(N-methyl-Z-hydroxyethylamino )-l,3,5-triazine.

2,4-dimethoxy-6-( N-methyl-2-hydroxyethylamino l,3,5-triazine,2,4-bis(dimethylamino)-6-(N-methyl-Z-hydroxyethylamino l ,3,5-triazine,2,4-diphenoxy-6-(N-methyl-Z-hydroxyethylamino)- 1,3,S-triazine, and

2,4-diphenoxy-6-(di-2-hydroxyethylamino)- l ,3,5-

triazine. Generally, the amount of s-triazine catalyst employed in theprocess of the subject invention will be from O. 1 part to 10 parts per100 parts of organic polyisocyanate.

The preparation of the triazine catalyst generally comprises condensingcyanuric chloride with the selected amine in the presence of aneutralizing amount of sodium hydroxide. Thus, for example,2,4,6-tris(diethanolamino)-s-triazine is prepared from the condensationof diethanolamine and cyanuric chloride in the presence of aneutralizing amount of sodium hydroxidc. The triazine compounds andtheir methods of preparation are known in the art and are more fullydescribed by Kaiser et al., Journal Of The American Chemical Society, V.73, p. 2984(l951), as well as in co-pending US. Pat. application Ser.No. 319,559 filed Dec. 29, 1972, now U.S. Pat. No. 3,806,475.

The urethane promoting catalysts which may be employed in the presentinvention are the metal or organometallic salts of carboxylic acid andtertiary amines. Representative of such compounds are: dibutyltindilaurate, dibutyltin diacetate, stannous octoate, lead octoate, cobaltnaphthenate, and other metal or organometallic salts of carboxylic acidsin which the metal is bismuth, titanium, iron, antimony, uranium,cadmium, aluminum, mercury, zinc or nickel as well as otherorganometallic compounds such as are disclosed in US. Pat. No.2,846,408. Tertiary amines such as triethylenediamine, triethylamine,diethylcyclohexylamine, dimethylethanolamine, methylmorpholine,trimethylpiperazine, N-ethylmorpholine and diethylethanolamine may alsobe employed as well as mixtures of any of the above. Preferredurethane-promoting catalysts are the tin salts of carboxylic acids suchas dibutyltin dilaurate and dibutyltin diacetate. Generally, the amountof the urethane-promoting catalyst employed in the process of thesubject invention will be from 0.1 part to IO parts per 100 parts oforganic polyisocyanate.

In accordance with the present invention, rigid cellular foams areprepared by the catalytic condensation of an organic polyisccyanate inthe presence of a catalytically sufficient amount of a triazine catalystand a urethane catalyst as hereinbefore defined.

The products which are produced in accordance herewith are rigidcellular foam plastics containing carbodiimide linkages, isocyanuratelinkages and urethane linkages. It is the carbodiimide linkages whoseformation provides the carbon dioxide blowing agent and which, togetherwith the isocyanurate linkages, imparts the excellent flame propertiesto the products.

The organic polyisocyanate used to prepare the carbodiimide foamcorresponds to the formula:

wherein R is a polyvalent organic radical which is either aliphatic,aralkyl, alkaryl, aromatic or mixtures thereof, and z is an integerwhich corresponds to the valence of R" and is at least two.Representative of the organic polyisocyanates contemplated hereinincludes. for example, the aromatic diisocyanates, such as 2,4- toluenediisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluenediisocyanate, crude toluene diisocyanate, methylene diphenyldiisocyanate, crude methylene diphenyl diisocyanate and the like; thearomatic triisocyanates such as 4,4,4"- triphenylmethane triisocyanate,2,4,6-toluene triisocyanates; the aromatic tetraisocyanates, such as4,4- dimethyldiphenylmethane-2.2'-5,5 '-tetraisocyanate, and the like;arylalkyl polyisocyanates. such as xylylene diisocyanate; aliphaticpolyisocyanates, such as hexam ethylene-1,o-diisocyanate, lysinediisocyanate methylester and the like; and mixtures thereof. Otherorganic polyisocyanates include polymethylene polyphenylisocyanate,hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate,naphthylenel ,5- diisocyanate, lmethoxyphenyl-2,4-diisocyanate, 4,4-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'- biphenyl diisocyanate,3,3-dirnethyl-4,4-biphenyl diisocyanate, and3,3-dimethyldiphenylmethane-4,4'- diisocyanate.

These polyisocyanates are prepared by conventional methods known in theart such as the phosgenation of the corresponding organic amine.

Still another class of organic polyisocyanates contemplated for useherein are the so-called quasiprepolymers". These quasi-prepolymers areprepared by reacting an excess of organic polyisocyanate or mixturesthereof with a minor amount of an active hydrogen containing compound asdetermined by the wellknown Zerewitinoff test. as described by Kohler inJournal Of The American Chemical Society, 49, 3181 1927). Thesecompounds and their methods of preparation are well known in the art.The use of any one specific active hydrogen compound is not criticalhereto, rather any such compound can be employed herein.

Suitable active hydrogen-containing groups as determined by theZerewitinofi method which are reactive with an isocyanate group includeOH, Nl-l, COOH, and SH. Examples of suitable types of organic compoundscontaining at least two active hydrogen-containing groups which arereactive with an isocyanate group are hydroxyl-terminated polyesters,polyalkylene ether polyols, hydroxyl-terminated polyurethane polymers,polyhydric polythioethers, alkylene oxide adducts ofphosphorus-containing acids, polyacetals, aliphatic polyols, aliphaticthiols including alkane, alkene and alkyne thiols having two or more SHgroups; diamines including both aromatic, aliphatic and heterocyclicdiamines, as well as mixtures thereof. Compounds which contain two ormore different groups within the above-defmed classes may also be usedin accordance with the process of the present invention such as, forexample, amino alcohols which contain an amino group and a hydroxylgroup. Also, compounds may be used which contain one SH group and one OHgroup as well as those which contain an amino group and a SH group.

Any suitable hydroxyl-terminated polyester may be used such as areobtained, for example, from polycarboxylic acids and polyhydricalcohols. Any suitable polycarboxylic acid may be used such as oxalicacid, malonic acid, succinic acid, glutaric acid, adipic acid,

pimelic acid. suberic acid, azelaic acid. sebacic acid. brassylic acid.thapsic acid. maleic acid. fumaric acid, glutaconic acid.oz-hydromuconic acid, B-hydromuconic acid, cx-butyl-a-ethyl-glutaricacid. a,B-diethylsuccinic acid. isophthalic acid, terephthalic acid.hemimellitic acid. and 1.4-cyclohexane-dicarboxylic acid. Any suitablepolyhydric alcohol. including both aliphatic and aromatic. may be usedsuch as ethylene glycol, l.3propylene glycol, l,2-propylene glycol. l.4-butylene glycol, l,3-butylene glycol. l.2-butylene glycol,l,5-pentanediol, l,4-pentanediol. l,3-pentanediol, 1,6hexanediol,1,7-heptanediol, glycerol. 1,] .ltrimethylolpropane. l,l,1-trimethylolethane, hexane- 1.2,6-triol, a-methyl glucoside,pentaerythritol, and sorbitol. Also included within the term polyhydricalcohol are compounds derived from phenol such as 2,-2-bis(4-hydroxyphenyl)propane, commonly known as Bisphenol A.

The hydroxyl-terminated polyester may also be a polyester amide such asis obtained by including some amine or amino alcohol in the reactantsfor the preparation of the polyesters. Thus. polyester amides may beobtained by condensing an amino alcohol such as ethanolamine with thepolycarboxylic acids set forth above, or they may be made using the samecomponents that make up the hydroxyl-terminated polyester with only aportion of the components being a diamine such as ethylene diamine.

Any suitable polyalkylene ether polyol may be used such as thepolymerization product of an alkylene oxide or of an alkylene oxide witha polyhydric alcohol. Any suitable polyhydric alcohol may be used suchas those disclosed above for use in the preparation of thehydroxyl-terminated polyesters. Any suitable alkylene oxide may be usedsuch as ethylene oxide, propylene oxide. butylene oxide, amylene oxide,and heteric or block copolymers of these oxides. The polyalkylenepolyether polyols may be prepared from other starting materials such astetrahydrofuran and alkylene oxidetetrahydrofuran copolymers',epihalohydrins such as epichlorohydrin; as well as aralkylene oxidessuch as styrene oxidev The polyalkylene polyether polyols may haveeither primary or secondary hydroxyl groups and, preferably, arepolyethers prepared from alkylene oxides having from two to six carbonatoms such as polyethylene ether glycols, polypropylene ether glycols,and polybutylene ether glycols. The polyalkylene polyether polyols maybe prepared by any known process such as, for example, the processdisclosed by Wurtz in 1859 and Encyclopedia OfChemr'cal Technology, Vol.7, pp. 257-262. published by Interscience Publishers, Inc. (l95l) or inUS. Pat. No. 1,922,459. Alkylene oxide adducts of Mannich condensationproducts are also useful in the invention.

Alkylene oxide adducts of acids of phosphorus which may be used includethose neutral adducts prepared from the alkylene oxides disclosed abovefor use in the preparation of polyalkylene polyether polyols. Acids ofphosphorus which may be used are acids having a P equivalency of fromabout 72% to about 95%. The phosphoric acids are preferred.

Any suitable hydroxyl-terminated polyacetal may be used such as, forexample. the reaction product of formaldehyde or other suitable aldehydewith a dihydric alcohol or an alkylene oxide such as those disclosedabove.

Any suitable aliphatic thiol including alkane thiols containing at leasttwo SH groups may be used such as l .Z-ethanedithiol,l,2-propanedithiol. 1 ,3- propanedithiol, and l,6-hexanedithiol;alkenethiols such as 2-butene-l,4-dithiol, and alkynethiols such as3-hexyne-l ,6-dithiol.

Any suitable polyamine may be used including aromatic polyamines such asp-aminoaniline. l,5- diaminonaphthalene, and 2,4-diaminotoluene;aliphatic polyamines such as ethylenediamine. 1,3- propylenediamine.1,4-butylenediamine. and 1.3-

butylenediamine, as well as substituted secondary derivatives thereof.

In addition to the above hydroxyl-containing compounds, other compoundswhich may be employed include graft polyols. These polyols are preparedby the in situ polymerization product of a vinyl monomer in a reactivepolyol medium and in the presence of a free radical initiator. Thereaction is generally carried out at a temperature ranging from about40C. to l50C.

The reactive polyol medium generally has a molecular weight of at leastabout 500 and a hydroxyl number ranging from about 30 to about 600. Thegraft polyol has a molecular weight of at least about 1500 and aviscosity of less than 40,000 cps. at 10% polymer concentration.

A more comprehensive discussion of the graft polyols and their method ofpreparation can be found in US. Pat. Nos. 3,383,351; 3,304,273;3,652,639, and in US. Pat. application Ser. No. 311,809 filed Dec. 4,1972 now US. Pat. No. 3,823,201, the disclosures of which are herebyincorporated by reference.

Also, polyols containing ester groups can be employed in the subjectinvention. These polyols are prepared by the reaction of an alkyleneoxide with an organic dicarboxylic acid anhydride and a compoundcontaining a reactive hydrogen atom. A more comprehensive discussion ofthese polyols and their method of preparation can be found in US. Pats.No. 3,585,185; 3,639,541, and 3,639,542. As is clear from the above, theparticular polyol ingredient employed in the preparation of thequasi-prepolymer is not a critical aspect of the present invention. Anycompound containing at least two reactive hydrogen atoms may be so used.

Another ingredient in the process of the subject invention is a polyol.Any of the polyols discussed above in connection with the preparation ofthe quasiprepolymers may be employed in the process of the subjectinvention. Generally from 1 part to 100 parts, preferably from 20 partsto parts, of said polyol per parts of organic polyisocyanate will beemployed in the process of the subject invention.

It is also possible to employ an isocyanate trimerization catalyst alongwith the triazine and urethane catalysts of the subject invention.Useful isocyanate trimerization catalysts include, for example,l,3,5-tris(N,N- dialkylaminoalkyl)-s-hexahydrotriazines; the alkyleneoxide and water adducts ofl,3,5-tris(n.n-dialkylaminoalkyD-shexahydrotriazines, 2,4,6-tris(dimethylaminomethyDphenol; 0-, por a mixture of oandp-dimethylaminomethylphenol, certain organotin compounds and the like.

l ,3,5-Tris(n,n-dialkylaminoalkyl )-s-hexahydrotriazine compounds haveheretofore been described as useful co-catalysts or isocyanatetrimerization catalysts. See US. Pat. No. 3,723,366, the disclosure ofwhich is hereby incorporated by reference. Preferred within this groupof hexahydrotriazine compounds is 1,3 ,5-tris-(N,N-dimethyl-3-aminopropyl )-s-hexahydrotriazinef The alkylene oxide andwater adducts of a 1.3.5-tris(N,N-dialkylaminoalkyl)-s-hexahyd1otriazine is presumably aquaternary ammonium hydroxide. These compounds are generally prepared byreacting equimolar amounts of the hexahydrotriazine, alkylene oxide andwater at a temperature of from about C. to 80C. for a period of fromabout 5 minutes to 2 hours. Preferred within this group of compounds isthe propylene oxide and water adduct of l,3,5-tris(N.N-dimethyl-3-aminopropyl)-s-hexahydrotriazine. See U.S. Pat. Nos.3,746,709 and 3,766,103, the disclosures of which are herebyincorporated by reference.

2,4,6-Tris(dimethylaminomethyl)phenol as well as 0-, pand a mixture ofoand p- (dimethylaminomethyl)phenol are known compounds which arecommercially available products sold by Rohm & Haas under the tradenames DMP-30 and DMP-lO.

The organotin compounds which are useful as isocyanate trimerizationcompounds are more particularly described in U.S. Pat. No. 3,396,167,the disclosure of which is hereby incorporated by reference.Specifically, the preferred compounds are triorganotin alkoxides orbis(triorganotin) oxide and, in particular, tri-nbutyltin methoxide,bis( tri-n-butyltin) oxide or bis(- triphenyltin) oxide With regard tothe phenol-type and organotintype isocyanate trimerization compounds,their use in the preparation of foams is more completely described inU.S. Pat. No. 3,717,596, the disclosure of which is also herebyincorporated by reference. Also useful trimerization catalysts areamines such as triethylene diamine.

The foams of the present invention are prepared by mixing together theorganic polyisocyanate, the polyol and the catalyst at an initiatingtemperature which, depending on the catalyst, will range from about 0C.to 150C. Under such conditions, carbon dioxide is generated, foamformation begins, and almost immediately an exotherm is developed withinthe reaction system. Alternatively, the foams may be prepared by addingthe catalyst to the polyisocyanate and the polyol and, when necessary,heating the mixture to the initiation temperature or separatelypre-heating the polyisocyanate, the polyol and the catalyst, and thenmixing the ingredients.

The present invention also contemplates the incorporation of additionalingredients in the foam formulation to tailor the properties thereof.Thus, plasticizers, such as tris( 2-chloroethyl) phosphate; surfactants,such as the silicone surfactants, e.g., alkylpolysiloxanes and polyalkylsiloxanes, may be employed in the invention. Further additionalingredients include auxiliary or supplemental blowing agents, such aswater or halohydrocarbons, as described in co-pending U.S. pat.application Ser. No. 169,526, filed Aug. 5, 1971. Also, inorto densityof from about one pound to forty pounds per cubic foot which exhibitexcellent flame properties, such as fire resistance, low smoke evolutionand excellent weight retention.

Following are specific, non-limiting examples which 15 are provided toillustrate the enumerated principles described herein. All parts are byweight unless otherwise indicated. In the examples, the compressivestrength properties of the foams were determined in accordance withASTM-l62 l. The flame retardant properties were determined by the ButlerChimney Test as described by Krueger et a1, SPE 25th Antec., Vol. Xlll,Detroit, Mich. 1967, pp. 1052-1057.

EXAMPLES 1-31 A series of foams was prepared by simultaneously adding aco-catalyst system to a reaction vessel equipped with a stirrer to whichhad been charged a polyisocyanate, a polyol and various optionalingredients such as a plasticizer, a surfactant and a blowing agent. Anexotherm was generated and foam formation followed soon after. Tables Iand [1, below, illustrate the details of the preparations, as well asthe physical properties of the resulting foams. In all cases, infrared35 spectroscopic analyses indicate that the foams exhibit carbodiimide,isocyanurate and urethane linkages. In Tables 1 and II, the followingabbreviations are employed:

TDI a mixture of /20 by weight 2,4-, 2,6-

40 tolylene diisocyanate MDl methylene diphenyl diisocyanate Polyol Apropylene oxide adduct of Mannich condensation product of one mole ofphenol, diethanolamine and formaldehyde (hydroxyl number of 530) PolyolB propylene oxide adduct of tris(diethanolaminomethyl)melamine (hydroxylnumber of 578) TMT 2,4,6-tris(N-methylethanolamino)-s-triazine 5O DMT2,4-bis(diethylamino)-6-(N-methyl-2- hydroxyethylamino)-s-triazine TDHl,3,5-tris(3-dimethylaminopropyl)-s-hexahydrotriazine T-12 dibutyltindilaurate TEDA triethylenediamine FYROL CEF tris(2-chloroethyl)phosphate DC-193 polysiloxane surfactant F-l 1B fluorotrichloromethaneF-l 13 l,1,2trichloro-l,2,2-trifluoroethane.

Table l Foam Preparation Parts by Weight lnit.

FYROL DC- Temp.

Example TDI MDI Polyol TMT DMT T-l2 TEDA TDH CEF 193 F-l 1B F-l 13 C.

1 1O A 22 8 3 1 2 l 23 15 3 10 90 A 28 7 2 l 2 l 15 22 Table l FoamPreparation-Continued lnit. Temp. C.

Parts by Weight F-llB FYRGL MDI Polyol TMT DMT T-i2 TEDA TDH CEF TDIExample mSSOOOOOOOO0000000000000000 7 8B8888800007-000O0 l l l l l lll2222 mmmmmm mmmmmw:

Table II Physical Properties Of Foams Compressive Butler Chimney TestTime Closed Strength at l 0% Deflection Foam of Density. Example pcfo00009988gonoo cn oosfluomwmm on swo BO 974862 oe- 2725on 751 soosssssssnsnsssssss .IZZZZZZLLLIZZ l l l l l l l l l l l l l l l 1 ll EXAMPLES32-46 mixture of styrene and acrylonitrile in a polyether polylcontaining approximately 0.3 mole of unsaturation. said polyether polyolhaving a hydroxyl num 60 and prepared by the reaction of ethylene oxidewith the her of 27 A series of foams was prepared following theprocedure described in EXAMPLE 1.

All formulations included 300 parts of polyphenyl polymethylenepolyisoheteric adduct of propylene oxide, allyl glycidyl ether andglycerol. The initiation temperature was 25C. T

cyanate, 6 parts of tris(2-chloroethyl) phosphate and 3 parts ofpolysiloxane surfactant as well as the other inphysical properties ofthe resulting foams are presented in Table [I]. [n all cases, infraredspectroscopic analyses gredients and amounts thereof set forth in Tableill.

The polyol (PolyolC) employed was a graft copolymer 65 indicate that thefoams contain carbodiimide, isocydispersion prepared by the in situpolymerization of a anurate and urethane linkages.

Table 111 Butler Chimney Comp. Tumb. Test Str. Friab. Closed Time Partsb\' Weight Time. sec. 10% 7: Cell Wt. Flame to Polyol F- Tack- Den. Def.Wt. Cont. Rel. H1. SX Example C T-l 2 DMT TDH 1 18 Cream Gel Free pct".psi. Loss 9? 7 in. sec. 32 45 3 l8 9 60 6 25 40 2.1 21.6 65 I 93 4 10 3345 2.7 18 9 60 8 30 60 2.1 21.6 63 100 93 34 45 3 18 8.1 60 8 35 60 2.122.2 66 102 92 6 10 35 45 3 9 60 10 35 60 2.1 20.9 67 102 95 6 I0 36 452.7 13 9 66 R 30 65 1.8 14.9 77 101 92 6 10 37 45 3 18 8.1 72 K 30 651.8 83 101 93 5 10 38 45 3 l5 9 66 8 35 70 1.9 16.9 67 102 92 5 10 39 603 l5 9 60 6 30 55 2.2 19.7 64 100 93 7 10 40 60 3 15 12 60 5 30 50 2.016.2 60 100 92 7 10 41 60 3 15 I5 60 4 30 40 2.0 16.2 67 100 92 7 1O 4260 3 I8 12 66 6 35 50 1.9 17.2 69 100 94 5 10 43 60 3 18 15 66 5 35 452.1 20.0 69 100 91 7 10 44 75 3 18 15 72 5 35 50 1.9 17.8 65 99 90 7 1045 75 3 18 I8 72 5 30 50 1.9 14.7 63 99 91 8 10 46 75 6 I8 9 72 5 30 601.9 16.7 59 99 91 7 l0 EXAMPLES 47-72 A series of foam was prepared inthe manner described in Example 1. In all cases. 300 parts of polypolyolprepared by the reaction of 12 moles of propylene oxide with theequimolar reaction product of tetrabromophthalic anhydride and a 400molecular weight propylene oxide adduct of pentamethylenepolyphenylisocyanate, 6 parts of tris( 2- erythritol chloroethyl)phosphate and 3 parts of siloxane surfac- Polyol G a 1500 molecularweight polyol prepared tant was employed. The particular polyol andcatalysts by the reaction of propylene oxide with glycerol employed, aswell as amounts thereof, are presented in Polyol H a 1050 molecularweight polypropylene Table IV, below. In all cases, the initiationtemperature glycol was 25C. and infrared spectroscopic analyses indicatePolyol l a 4500 molecular weight polyol prepared that the foams exhibitcarbodiimide, isocyanurate and by capping with ethylene oxide :1propylene oxide urethane linkages. The abbreviations DMT, TDH and adductof trimethylolpropane, said polyol having F-l 1B are described above.The following new abbrevian ethylene oxide content of 9% ations are usedin Table IV: Polyol J a 730 molecular weight propylene oxide DBTDAdibutyltin diacetate adduct of trimethylolpropane DMP-lO mixture of oandp- Polyol K a 1500 molecular weight polyol prepared(dimethylaminomethyl)phenol by capping with ethylene oxide 21 propyleneoxide Polyol D ethylene oxide adduct of Bisphenol A, adduct of glycerol,said polyol having an ethylene hydroxyl number of approximately 220oxide content of approximately 67% by weight Polyol E a 500 molecularweight propylene oxide Polyol L a 1000 molecular weight polyol preparedadduct of Bisphenol A, hydroxyl number of apby capping with ethyleneoxide a propylene oxide proximately 220 adduct of propylene glycol. saidadduct having an Polyol F a 985 molecular weight ester-containingethylene oxide content of 67% by weight.

Table [V Butler Chimney Comp. Tumb. Test Str. Friab. Closed Time Time,sec. 10% 71 Cell Wt. Flame to DMP- Tack Den. Def. Wt. Cont. Rel. Htv SXEx. Polyol DMT TDH DBTDA T-l2 10 F 1 18 Cream Gel Free pcf. psi Loss 1 Zin. sec. 47 D 6 3 3 60 4 27 81 1.9 21.0 35 115 93 5 10 48 45 D 33 3 3 604 21 110 1.8 19.2 51 107 90 6 10 49 45 E 6 3 2.1 60 10 40 110 1.7 17.024 95 9| 6 10 50 E 6 3 3 66 9 34 130 1.7 13.4 23 96 90 6 10 51 E 6 3 2.166 8 35 125 1.6 17.0 15 98 92 6 10 52 313: 12 1.5 0.9 18 60 5 50 63 1.717.0 44 96 84 8 10 53 2(1)): 6 1.5 0.6 12 60 5 42 50 2.0 20.0 22 95 8310 10 30 A 55 45 G 9 6 0.9 60 I2 55 135 1.9 22.0 57 98 4 10 56 60 G 9 60.9 66 12 50 125 1.9 21 51 98 91 5 10 57 75 G 9 4.5 0.9 72 14 55 225 2.016 62 99 91 7 10 58 45 H 9 6 0.9 60 12 55 160 1.9 21 63 94 5 10 59 60 H9 4.5 0.9 66 13 60 225 1.8 17 67 I00 96 4 10 60 75 H 9 4.5 0.9 72 13 60230 1.8 15 66 97 90 6 10 61 451 9 12 1.2 66 9 45 75 1.9 18 60 97 86 6 1362 601 9 9 0.9 72 15 65 1.8 16 65 96 89 8 10 63 75 1 9 9 0.6 78 14 701.8 14 60 102 86 9 11 64 45 1 9 6 0.6 66 15 55 1.7 20 47 108 84 6 10Table lV-Continued Butler Chimney Comp. Tumh. Test Str. Friab. ClosedTime I Time. sec. 10% 7r Cell Wt. Flume to I DMP Tuck Den. Del. Wt.Cont. Ret Ht. SX Ex. Polyol DMT TDH DBTDA T-l2 I Fl IB Cream Gel Freepcf. psi. Loss 7i '4 in. sec.

65 60 J 9 6 0.3 66 I 50 I80 L8 20 42 I13 90 I0 I l 66 75 J 9 6 0.3 72 I555 I85 L8 18 38 I 86 8 I0 67 45 K 6 4.5 0.3 60 24 55 I30 2.0 21 68 96 954 I0 68 60 K 6 3 0.3 66 I9 70 220 L9 24 53 l I I 94 4 I0 69 75 K 6 3 0.372 9 60 240 [.8 I7 46 I03 94 4 I0 70 45 L 3 9 0.3 60 I8 47 I40 2.0 22 57I02 94 4 I0 H 60 L 3 6 0.3 66 7 46 200 2.0 [8 44 97 93 6 I0 72 75 L 34.5 0.3 72 8 50 260 1.9 I4 52 99 93 5 I0 X EXAMPLES 73-96 I A series offoams was prepared employing various C metal and organometallic salts ofcarboxylic acids. The initiation temperature was 10C. and eachformulation 20 N N contained in addition to that illustrated in Table Vtwo I CR CR OH parts of DMT, one part of TDH and one part of silox- CC-..N ane surfactant. In the Table, Pb-Oct. stands for lead oc- X Rtoate. All other abbreviations are as defined above. N

Table V Butler Chimney Comp. Tumbl. Test Parts by Weight Str. Friab.Closed Time Urethane Catalyst Time. sec. 10% Cell Wt. Flame to Polyol T-T- Pb- DBT- F- Tack Den. Defl. Wt. Cont. Rel. Ht. SK Exum- PA Pl TDI A12 9 Oct. DA I 18 Cream Gel. Free pcf. psi. Loss X in. sec.

ple

73 90 10 I0 2 l6 7 20 65 2.0 34.4 45 I02 94 9 I0 74 90 l0 l0 2 I6 4 90I20 l.9 25.0 85 99 39 IO I0 75 90 l0 l0 2 l6 4 35 I05 2.0 28.9 73 I0] 909 I0 76 90 I0 I0 2 I6 7 3O 65 1.9 27.3 52 I00 85 I0 I0 77 90 I0 [5 2 l34 I2 30 2.3 45.3 2| I03 93 9 I0 78 90 I0 I5 2 I6 3 20 30 L9 25.5 41 I0077 9 I l 79 90 l0 l5 2 I6 3 I6 35 2.0 26.4 44 I00 85 I0 10 80 90 IO I5 2I6 5 I8 25 1.9 30.6 25 I00 78 I0 I I 81 90 I0 20 2 I6 3 6 2.2 40.7 I4I02 84 9 II 82 90 I0 2 I6 3 I0 I0 2.0 456 I5 lOl 85 9 I0 83 90 I0 20 2I6 3 I2 35 2.] 29.0 I00 8] 10 ll 84 90 I0 20 2 I6 5 I4 25 L9 32.4 I7 I0l71 l I I3 85 I00 0 l0 2 I8 5 90 L9 23.6 50 I02 84 IO I0 86 I00 0 I0 2 I64 90 I20 I.9 23.5 8| 99 78 IO I2 87 I00 0 I0 2 I8 4 45 90 2.0 20.1 78I0] 89 IO I0 88 I00 0 I0 2 l6 6 55 2.0 30.5 42 I0] 86 I0 I0 89 I00 0 I52 I6 4 I2 30 2.1 25.3 20 99 86 I0 I I 90 I00 0 I5 2 I6 4 25 25 2.0 30.332 I00 76 ll I0 9] I00 0 I5 2 I8 4 25 2.0 25.9 43 IOI 84 I0 IO 92 I00 0l5 2 I6 5 25 30 2.] 38.9 23 I00 92 8 I0 93 I00 0 20 2 l6 4 8 I5 2.2 384I2 I02 79 I0 I2 94 I00 0 20 2 l8 3 l0 15 1.9 36.8 I5 I00 71 II I2 95 I000 20 2 l8 3 20 45 1.9 32.2 20 l0l 77 I I I I 96 I00 0 20 2 l6 4 20 252.! 39.7 13 99 80 I I I2 The embodiments of the invention in which anexclusive property or privilege is claimed are defined as follows:

1. A process for the preparation of a cellular foam characterized bycarbodiimide-isocyanurate-urethane linkages which comprises reacting anorganic polyisocyanate and a polyol in the presence of a catalyticallysufficient amount of a catalyst system comprising wherein R is hydrogenor lower alkyl of from I to 10 carbon atoms, R is CR CR OH or loweralkyl of from I to 12 carbon atoms, X is NR alkoxy of from I to 12carbon atoms, phenoxy atoms, alkyl of from I to 12 carbon atoms, phenyl,hydroxyl, halogen, aziridyl, pyrrolidyl, piperidyl, or N-alkylpiperazyl,and

b. a compound which promotes urethane linkages.

2. The process of claim 1 wherein the organic polyisocyanate is selectedfrom the group consisting of toluene diisocyanate, methylene diphenyldiisocyanate, polyphenyl polymethylene polyisocyanate and mixturesthereof.

3. The process of claim 1 wherein the polyol is an alkylene oxidecondensate of an organic compound having from 2 to 6 reactive hydrogenatoms.

8. The process of claim I conducted in the presence of a fluorocarbonblowing agent.

9. The process of claim I conducted in the presence of tris(2-chloroethyl) phosphate.

10. The process of claim I conducted in the presence of l ,3.5-tris(B-dimethylaminopropyl)-s-hexahyd rotriazme.

1. A PROCESS FOR THE PREPARATION OF A CELLULAR FOAM CHARACTERIZED BYCARBODIMIDE-ISOCYANURATE-URETHANE LINKAGES WHICH COMPRISES REACTING ANORGANIC POLYISOCYANATE AND A POLYOL IN THE PRESENCE OF A CATALYTICALLYSUFFICIENT AMOUNT OF A CATALYST SYSTEM COMPRISING A. AN S-TRIAZINECOMPOUND SELECTED FROM THE GROUP CONSISTING OF2,4,6-TRIS(DIETHANOLAMINO)-S-TRIAZINE,2,4,6-TRIS(DIISOPROPANOLAMINO)-S-TRIAZINE,2,4,6-TRIS(DIBUTANOLAMINO)-S-TRIAZINE,2,4,6-TRIS(N-METHYLETHANOLAMINE)-S-TRIAZINE, AND UNSYMMETRICALLYSUBSTITUTED TRIAZINES OF THE FORMULA:
 2. The process of claim 1 whereinthe organic polyisocyanate is selected from the group consisting oftoluene diisocyanate, methylene diphenyl diisocyanate, polyphenylpolymethylene polyisocyanate and mixtures thereof.
 3. The process ofclaim 1 wherein the polyol is an alkylene oxide condensate of an organiccompound having from 2 to 6 reactive hydrogen atoms.
 4. The process ofclaim 1 wherein the s-triazine compound is 2,4,6-tris(diethanolamino)-s-triazine.
 5. The process of claim 1 whereinthe s-triazine compound is 2,4-bis(diethylamino)-6-(N-methyl-2-hydroxyethylamino)-s-triazine.
 6. Theprocess of claim 1 wherein the compound which promotes urethane linkagesis dibutyltin dilaurate.
 7. The process of claim 1 wherein the compoundwhich promotes urethane linkages is dibutyltin diacetate.
 8. The processof claim 1 conducted in the presence of a fluorocarbon blowing agent. 9.The process of claim 1 conducted in the presence of tris(2-chloroethyl)phosphate.
 10. The process of claim 1 conducted in the presence of1,3,5-tris(3-dimethylaminopropyl)-s-hexahydrotriazine.